JP2003015296A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification type positive type photoresist composition excellent in various characteristics such as resolving power, margin for exposure, edge roughness of a pattern and density dependence. SOLUTION: The positive type photoresist composition contains (A) at least two photo-acid generators which are selected from sulfonates in which each of cationic moieties comprises iodonium or sulfonium and each of anionic moieties comprises an anion of the formula RFSO3 <-> (where RF is a 1-20C fluorine substituted alkyl group), have a difference between the numbers of carbon atoms in the groups RF of the anionic moieties in the range of 2-15 and generate acids when irradiated with active light or radiation and (B) a resin which contains specified repeating units and is decomposed by the action of the acids to increase its alkali solubility.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used in an ultra-microlithography process such as production of an ultra-LSI or a high-capacity microchip and other photofabrication processes. More specifically, it relates to a positive photoresist composition capable of forming a highly detailed pattern by using light having a deep ultraviolet region including excimer laser light, particularly light having a wavelength of 250 nm or less.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having line widths of half micron or less. Has become. In order to meet the need, the wavelength of the exposure apparatus used for photolithography has become shorter and shorter, and now, excimer laser light (XeCl, KrF, ArF, etc.) with a short wavelength in far ultraviolet rays is being used.
Is being considered. A chemically amplified resist is used as a pattern for lithography in this wavelength region.

As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced for the purpose of imparting dry etching resistance has been proposed. As such a resin, a monomer having a carboxylic acid moiety such as acrylic acid or methacrylic acid or a monomer having a hydroxyl group or a cyano group in the molecule is copolymerized with a monomer having an alicyclic hydrocarbon group. Resin.

On the other hand, in addition to the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate-based monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. ing. In addition, JP-A-9
-73173, JP-A-9-90637, JP-A-10
JP-A-161313 discloses an acid-sensitive compound containing an alkali-soluble group protected by a structure containing an alicyclic group and a structural unit capable of eliminating the alkali-soluble group with an acid to make it alkali-soluble. The resist material that was used is described. Further, a resin in which a hydrophilic 5-membered or 6-membered lactone group is introduced into a resin having these alicyclic groups for the purpose of improving affinity to an alkali developing solution and adhesion to a substrate is disclosed in JP-A 9-90637, JP-A-10-207069, and JP-A-10-274852.
And JP-A-10-239846. Even with the techniques described above, in the photoresist composition (particularly, the photoresist for exposure to deep ultraviolet rays), there still exist improvements due to the resin containing an acid-decomposable group. However, these compositions have a problem that the resolution of the pattern is hindered by factors such as the edge roughness of the line pattern. Here, the edge roughness is
The top and bottom edges of the resist line pattern are
Due to the characteristics of the resist, it irregularly fluctuates in the direction perpendicular to the line direction, so that the edges appear to be uneven when the pattern is viewed from directly above.

Furthermore, there is room for improvement in the problem of sparse / dense dependence. Since various patterns are included in the trend of recent devices, various performances are required for resists, and one of them is sparse / dense dependence. That is, the device has a portion where lines are densely arranged, a pattern having a wider space as compared with a line, and an isolated line. Therefore, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and it is the current situation that the solution method using resist is not clear. Particularly, in the above-mentioned resist system containing an alicyclic group, the performance difference between the isolated pattern and the dense pattern is remarkable, and improvement is desired.

Further, the conventional resist composition has a problem of exposure amount dependency that the pattern line width is changed by a subtle change of the exposure amount, and a resist composition having a wide exposure margin with less line width change is available. It was wanted.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a chemically amplified positive photoresist composition which is excellent in resolution, exposure margin, edge roughness of pattern, and sparse / dense dependence. is there.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to the constituent material of a resist composition in a positive type chemical amplification system, and as a result, use a specific photo-acid generator and an acid-decomposable resin having a lactone structure. As a result, they have found that the object of the present invention can be achieved, and have reached the present invention. That is, the above object is achieved by the following configurations.

(1) (A) The cation part is composed of iodonium or sulfonium, and the anion part is R ^F SO.
₃ ^- (wherein, R ^F is a fluorine-substituted alkyl group having 1 to 20 carbon atoms) are selected from sulfonic acid salt that consists of an anion represented by, and the anion moiety R ^F
A photoacid generator capable of generating an acid upon irradiation with at least two actinic rays or radiations having a carbon number difference of 2 to 15, and (B) the following general formulas (I-1) to (I-4 (4) A positive photoresist composition comprising a resin containing a repeating unit having a group represented by at least any one of (1) to (4) which is decomposed by the action of an acid to increase the solubility in alkali.

[0010]

[Chemical 6]

In the general formulas (I-1) to (I-4); R ₁ to
R _{5 s} may be the same or different and each represents a hydrogen atom or an alkyl group, cycloalkyl group or alkenyl group which may have a substituent. Two of R _{1 to} R ₅ may combine with each other to form a ring.

(2) As for the component (A), a photoacid generator having a relatively large carbon number of R ^F is R in the anion part.
^An anion moiety is selected from the group of photoacid generators in which ^F is a linear fluorine-substituted alkyl group having 4 to 20 carbon atoms, and R ^F has a relatively small number of carbon atoms. The positive photoresist composition as described in (1) above, wherein R ^F is selected from the group of photoacid generators having a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms. .

(3) In the above (1) or (2), the cation portion of at least one photoacid generator is represented by the following general formula (I), (II) or (III). The positive resist composition as described above.

[0014]

[Chemical 7]

In the above general formulas (I) to (III): R _{1 to} R ₃₇
Are the same or different and each is a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or -S-.
Represents an R ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. In addition, R _{1 to} R ₁₅ , R
Two or more of _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other and selected from a single bond, carbon, oxygen, sulfur, and nitrogen.
It may form a ring containing two or more species.

(4) An alkali in which the resin of (B) is further protected with at least one group selected from the groups having an alicyclic hydrocarbon structure represented by the following general formulas (pI) to (pVI). The positive photoresist composition as described in (1) to (3) above, which contains a repeating unit having a soluble group.

[0017]

[Chemical 8]

In the general formulas (pI) to (pVI); R ₁₁ is
It represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Represents R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that R _{12 to} R ₁₄
At least one of them, or either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that R ₁₇
At least one of R ₂₁ to R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ has 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ is an aliphatic group. Represents a cyclic hydrocarbon group.

(5) The above general formulas (pI) to (pVI)
The positive photoresist composition as described in (1) to (4) above, wherein the group containing an alicyclic hydrocarbon structure represented by the following is a group represented by the following general formula (pIa). .

[0020]

[Chemical 9]

In the general formula (pIa), R₂₈Has a substituent
Represents an optionally substituted alkyl group. R ₂₉~ R₃₁Is the same
May be different, a hydroxy group, a halogen atom,
A carboxy group or an optionally substituted
Alkyl group, cycloalkyl group, alkenyl group, alkoxy group
Represents a Si group, an alkoxycarbonyl group or an acyl group.
p, q, and r each independently represent an integer of 0 or 1 to 3.
You

(6) The positive type as described in any one of (1) to (5) above, wherein the resin (B) contains a repeating unit represented by the following general formula (a). Photoresist composition.

[0023]

[Chemical 10]

In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R _{32 to} R _{34, which} may be the same or different, each represents a hydrogen atom or a hydroxyl group. At least one of R _{32 to} R ₃₄ represents a hydroxyl group.

Further, the following embodiments are also preferable. (7) The positive photoresist composition as described in any of (1) to (6) above, which further comprises (C) an acid diffusion inhibitor.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. <(A) Compound that Generates Acid by Irradiation with Actinic Rays or Radiation (also referred to as photoacid generator or component (A))> In the present invention, the cation moiety is composed of iodonium or sulfonium as a photoacid generator, Anion part is R ^F SO
₃ ^- (wherein, R ^F is a fluorine-substituted alkyl group having 1 to 20 carbon atoms) are selected from sulfonic acid salt represented by, and the difference of the number of carbon atoms in R ^F anion portion 2 At least two photoacid generators in the range of 15 are used.

As the photoacid generator having a relatively large number of carbon atoms in R ^F , a photoacid generator having a linear fluorine-substituted alkyl group having an R ^{F in the} anion part in the range of 4 to 20 carbon atoms can be used. The photo-acid generator selected from the group of agents having a relatively small carbon number of R ^F is a photo-acid generator having a linear fluorine-substituted alkyl group in which R ^F of the anion part is in the range of 1 to 5 carbon atoms. It is particularly preferred that it is selected from the group of acid generators.

Further, the cation moiety has the following general formula (I):
The photoacid generator represented by (II) or (III) is preferable.

[0029]

[Chemical 11]

In the above general formulas (I) to (III): R _{1 to} R ₃₇
Are the same or different and each is a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or -S-.
Represents an R ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. In addition, R _{1 to} R ₁₅ , R
Two or more of _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other and selected from a single bond, carbon, oxygen, sulfur, and nitrogen.
It may form a ring containing two or more species.

In the present invention, the cation part is composed of iodonium or sulfonium and the anion part is R ^F SO.
₃ ^- (wherein, the R ^F is, a fluorine-substituted alkyl group having 1 to 20 carbon atoms) is more photoacid generator is selected from the sulfonic acid salt is composed of an anion represented by Used. The fluorine-substituted alkyl group represented by R ^F may be linear, branched or cyclic.
Preferred R ^F is a fluorine-substituted linear alkyl group represented by CF ₃ (CF ₂ ) y, where y is an integer of 0 to 9. The alkyl group as R ^F may have a substituent such as a hydroxyl group and a cyano group, and —O—, —S—,
-CO-, -COO-, -NHCO-, -CONHSO
_It may contain a divalent linking group such as 2-. In this case, the carbon number of R ^F includes the carbon number of the linking group. Further, the alkyl group represented by R ^F may be substituted with one or more fluorine atoms, and preferably the hydrogen atom of the carbon atom at the α-position of sulfonic acid is substituted with a fluorine atom.

The composition of the present invention comprises, as a photoacid generator, at least two (pair) photoacid generators having a difference in carbon number of R ^F from 2 to 15, preferably from 3 to 7. contains. For example, when three kinds of photo-acid generators having carbon numbers of R ^F are 3, 4, and 5, respectively, a pair of photo-acid generators having a difference in carbon number of R ^F in the range of 2 to 15 are used. It exists and meets the above conditions. Further, the carbon numbers of R ^F are 2, 6, and 8 respectively.
When three kinds of photoacid generators are used, three pairs exist and the above conditions are satisfied. Among the photo-acid generators containing at least two kinds described above, the total amount of the photo-acid generators forming a pair is preferably 50 to 100 mol% with respect to the total photo-acid generators, and more preferably 70-100 mol%
Is.

The positive resist composition of the present invention comprises a plurality of photoacid generators satisfying the above conditions, together with the above-mentioned (B) specific resin (B-1) or polymer (B-2) described in detail below. By containing it, in microphotofabrication using ArF excimer laser light, various properties such as resolving power, exposure margin, edge roughness of pattern, and dependency of density are provided.

In a preferred embodiment, R ^F of the anion moiety
Of at least one pair of photoacid generators having a carbon number difference of 2 to 15 in the range of 2 to 15, R ^F of the photoacid generator having a relatively large carbon number of R ^F is 4 to 20 carbon atoms. A photo-acid generator having a linear fluorine-substituted alkyl group (hereinafter, this photo-acid generator may be abbreviated as “photo-acid generator A1”) and R ^F having a relatively small number of carbon atoms; R ^F is a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms (hereinafter, this photoacid generator may be abbreviated as “photoacid generator A2”). Further, the molar ratio of the photoacid generator A1 and the photoacid generator A2 (A1
/ A2) is 90/10 to 10/90, especially 80/2
It is preferably 0 to 20/80.

The cation moiety of the photoacid generator is preferably represented by the above general formulas (I) to (III). General formula (I)-
In (III), the linear or branched alkyl group for R _{1 to} R ₃₈ may have a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, t
-C1-C4 thing like a butyl group is mentioned. The cyclic alkyl group may have a substituent,
Examples thereof include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group. R ₁ ~
Examples of the linear or branched alkoxy group for R ₃₇ include, for example,
Methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-
Examples thereof include those having 1 to 4 carbon atoms such as butoxy group and t-butoxy group. As the cyclic alkoxy group, a cyclopentyloxy group, for example, a cyclopentyloxy group,
A cyclohexyloxy group may be mentioned. Examples of the halogen atom of R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group of R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group and a naphthyl group. As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms are preferable. , Cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of ₃₇ , one or two selected from a single bond, carbon, oxygen, sulfur, and nitrogen, which is formed by combining two or more.
Examples of the ring containing at least one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, and a pyrrole ring.

Further, a photoacid generator represented by the following general formula (IV) or (V) is also preferable.

Examples of the compound having a phenacylsulfonium salt structure which generates an acid upon irradiation with actinic rays or radiation include the compounds represented by the following general formula (IV).

[0039]

[Chemical 12]

R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. R
_6c and R _7c each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rx and Ry each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. R _{1c to} R _7c
Any two or more of them, and Rx and Ry may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, an ester bond or an amide bond. X ⁻ represents R ^F SO ₃ ⁻ . R ^F is the same as that described above.

The alkyl group as R _{1c to} R _5c is a straight chain,
It may be branched or cyclic, and has, for example, 1 to 1 carbon atoms.
10 alkyl groups, preferably linear and branched alkyl groups having 1 to 5 carbon atoms (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group). And a cyclic alkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group). The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic. For example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, a methoxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group), a cyclic alkoxy group having 3 to 8 carbon atoms (for example, a cyclopentyloxy group,
And a cyclohexyloxy group). Preferably, any of R _{1c to} R _{5c is} a linear, branched or cyclic alkyl group, or a linear, branched or cyclic alkoxy group,
More preferably, the sum of carbon numbers of R _1c to R _5c is 2 to 15. Thereby, the solvent solubility is further improved, and the generation of particles during storage is suppressed.

_Examples of the alkyl group as R _6c and R _7c include the same as the alkyl group as R _{1c to} R _5c . Examples of the aryl group may include an aryl group having 6 to 14 carbon atoms (for example, a phenyl group). Alkyl groups as Rx and Ry are R _1c
The same examples of the alkyl group as R 5 to R _5c can be mentioned. 2-oxoalkyl group include a group having> C = O at the 2-position of the alkyl group as R _1c to R _5c. As the alkoxy group in the alkoxycarbonylmethyl group, the same alkoxy groups as R _{1c to} R _5c can be mentioned. Examples of the group formed by combining Rx and Ry include a butylene group and a pentylene group.

The compound of formula (IV) is capable of forming a ring.
The three-dimensional structure is more fixed and the optical resolution is improved. R_1c~
R_7cWhen any two of them combine to form a ring structure
About R_1c~ R_5cAny one of and R_6cAnd R_7c
Any one of the above bonds to form a single bond or a linking group,
It is preferable to form a ring, especially R_5cAnd R_6cOr R _7c
When are combined to form a single bond or a linking group to form a ring
Is preferred. The linking group may have a substituent.
Alkylene group, alkenylene which may have a substituent
Group, -O-, -S-, -CO-, -CONR- (R is
Hydrogen atom, alkyl group, acyl group), and these
Groups formed by combining two or more of
, Optionally substituted, alkylene group, oxygen source
Child-containing alkylene group, sulfur atom-containing alkylene group
preferable. As the substituent, an alkyl group (preferably carbon
Prime number 1 to 5), aryl group (preferably having 6 to 1 carbon atoms)
0, eg phenyl group, acyl group (eg 2 carbon atoms)
To 11) and the like. Also, methylene
Group, ethylene group, propylene group, -CH₂-O-, -C
H₂A linking group forming a 5- to 7-membered ring such as -S- is preferred.
, Ethylene group, -CH₂-O-, -CH₂-S- etc.
A linking group forming a 6-membered ring is particularly preferable. 6 members
The carbonyl plane and C-S + sig are formed by forming a ring.
Ma bond becomes closer to vertical, and the orbital interaction causes light
The resolution is improved. Also, R_1c~ R_7cAnd Rx and Ry
At some position, attached through a single bond or a linking group, the formula
It may be a compound having two or more (IV) structures.
Yes.

The sulfonium salt having no aromatic ring is a salt having sulfonium represented by the following formula (V) as a cation.

[0045]

[Chemical 13]

In the formula, R ^{1b to} R ^3b each independently represents an aromatic ring-free organic group. Here, the aromatic ring also includes an aromatic ring containing a hetero atom. X
^- is, R ^F SO ₃ ^- represents a. R ^F is the same as that described above.

The aromatic ring-free organic group as R ^{1b to} R ^3b generally has 1 to 30 carbon atoms, preferably 1 carbon atom.
~ 20. R ^{1b to} R ^3b are each independently preferably an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group or a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group, Alkoxycarbonylmethyl group, most preferably linear, branched 2-
It is an oxoalkyl group. The alkyl group as R ^{1b to} R ^3b may be linear, branched, or cyclic, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group). Group, butyl group, pentyl group) and cyclic alkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group). The 2-oxoalkyl group as R ^{1b to} R ^3b may be linear, branched or cyclic,
Preferred is a group having> C = O at the 2-position of the above alkyl group. The alkoxy group in the alkoxycarbonylmethyl group as R ^{1b to} R ^3b is preferably an alkyl group having 1 to 5 carbon atoms (methyl group,
And ethyl group, propyl group, butyl group, pentyl group). R ^{1b to} R ^3b may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. R ^{1b to} R ^3b
Two of them may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. The group formed by combining two members out of R ^{1b to} R ^3b is an alkylene group (for example,
Butylene group and pentylene group). From the viewpoint of photoreactivity, a group in which any one of R ^{1b to} R ^3b has a carbon-carbon double bond or a carbon-oxygen double bond is preferable. R ^{1b of the} compound represented by the general formula (V)
At least one of R ^3b are, may take at least one coupling to the structure of R ^1b to R ^3b of the general formula (V) Other compounds of the general.

Photoacid generator A that can be used in the present invention
Specific examples (A1-1) to (A1-91) of No. 1 are shown below.

[0049]

[Chemical 14]

[0050]

[Chemical 15]

[0051]

[Chemical 16]

[0052]

[Chemical 17]

[0053]

[Chemical 18]

[0054]

[Chemical 19]

[0055]

[Chemical 20]

[0056]

[Chemical 21]

[0057]

[Chemical formula 22]

[0058]

[Chemical formula 23]

[0059]

[Chemical formula 24]

Photoacid generator A that can be used in the present invention
Specific examples (A2-1) to (A2-74) of No. 2 are shown below.

[0061]

[Chemical 25]

[0062]

[Chemical formula 26]

[0063]

[Chemical 27]

[0064]

[Chemical 28]

[0065]

[Chemical 29]

[0066]

[Chemical 30]

[0067]

[Chemical 31]

[0068]

[Chemical 32]

[0069]

[Chemical 33]

Among them, the photoacid generator A1 is CF
Compounds that generate ₃ (CF ₂ ) ₃ SO ₃ H and CF ₃ (CF ₂ ) ₇ SO ₃ H are preferable, and CF ₃ S is used as the photoacid generator A 2.
Compounds generating O ₃ H and CF ₃ (CF ₂ ) ₃ SO ₃ H are preferable. A preferred combination of the photoacid generators A1 and A2 (photoacid generators A1 / A2, represented by generated acid) is CF ₃ (CF ₂ ) ₃ SO ₃ H / CF ₃ SO ₃ H, CF
₃ (CF ₂ ) ₇ SO ₃ H / CF ₃ SO ₃ H, CF ₃ (CF ₂ ) ₇
SO ₃ H / CF ₃ (CF ₂ ) ₃ SO ₃ H.

In the present invention, the addition amount of the photoacid generator as the component (A), that is, the total amount of two or more photoacid generators forming a pair is based on the solid content in the composition. It is usually used in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 5% by weight. Addition amount of photo-acid generator is 0.0
If it is less than 01% by weight, the sensitivity is low, and if it is more than 40% by weight, the light absorption of the resist becomes too high, the profile is deteriorated and the process (particularly baking) margin is narrowed, which is not preferable.

The sulfonium salt of the photoacid generator A1 or the photoacid generator A2 corresponds to the triarylsulfonium halide obtained by reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenyl sulfoxide. A method of salt exchange with sulfonic acid, or substituted or unsubstituted phenyl sulfoxide and the corresponding aromatic compound with methanesulfonic acid /
It can be synthesized by a method of condensation and salt exchange using an acid catalyst such as diphosphorus pentoxide or aluminum chloride, or a method of condensation and salt exchange between a diaryl iodonium salt and a diaryl sulfide using a catalyst such as copper acetate. on the other hand,
The iodonium salt of the photoacid generator A1 or the photoacid generator A2 is reacted with an aromatic compound using a periodate salt,
It can be synthesized by salt exchange of the obtained iodonium salt with the corresponding sulfonic acid. As the sulfonic acid or sulfonate used for salt exchange, a commercially available sulfonic acid can be used as it is, or can be obtained by hydrolysis of a sulfonic acid halide.

In the positive resist composition of the present invention, a photo-acid generator other than the compounds specified above can be used in combination. As the photoacid generator that can be used in combination, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
Known light used for photo-decoloring agents of dyes, photo-discoloring agents, micro resists, etc. (ultraviolet rays of 400 to 200 nm, deep ultraviolet rays, particularly preferably g-line, h-line, i-line)
Ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a molecular beam or an ion beam to generate an acid, and a mixture thereof can be appropriately selected and used.

Other photoacid generators that can be used in combination include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and other onium salts, organic halogen compounds, organic metal / Examples include organic halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid by photolysis represented by iminosulfonates, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. be able to. Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into the main chain or side chain of a polymer can be used together.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and European Patent 126,712 can be used in combination with the compounds capable of generating an acid by light. Among the compounds that decompose to generate an acid upon irradiation with actinic rays or radiation, those that are particularly effectively used include the following general formula (PAG3), general formula (PAG4), general formula (PAG6), or general formula (PAG6). The compound shown by PAG7) can be mentioned.

[0076]

[Chemical 34]

In the general formulas (PAG3) and (PAG4), A
r ¹ and Ar ² are the same or different and each represents a substituted or unsubstituted aryl group. Preferable substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group and a halogen atom. R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ are
The same or different, substituted or unsubstituted alkyl group,
Indicates an aryl group. Of these, an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof are preferable. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and an alkyl group for the alkyl group. Carbon number 1
To alkoxy groups, carboxyl groups, and alkoxycarbonyl groups.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Alkane sulfonic acid that may be substituted, perfluoroalkane sulfonic acid, benzene sulfonic acid that may be substituted, naphthalene sulfonic acid, anthracene sulfonic acid,
Examples thereof include camphor sulfonic acid, but are not limited thereto. Preferred are alkanesulfonic acid, perfluoroalkanesulfonic acid, alkyl-substituted benzenesulfonic acid, and pentafluorobenzenesulfonic acid. Two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ and Ar ^{2 are also included.}
May be bonded via their respective single bonds or substituents.

In the general formulas (PAG6) and (PAG7), R
²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0080]

[Chemical 35]

[0081]

[Chemical 36]

In the present invention, the photoacid generator used in combination is preferably one represented by the above formula (PAG-7). These photoacid generators that can be used in combination are used in an amount of 5% by weight or less, preferably 2% by weight or less, based on the solid content of the composition.

<Resin which is decomposed by the action of (B) acid to increase its solubility in alkali> Resin which is decomposed by the action of (B) acid used in the composition of the present invention and whose solubility in alkali is increased (hereinafter , Also simply referred to as “resin of (B)” includes a repeating unit having a group represented by the above general formulas (I-1) and (I-4). General formula (I-1)-
In (I-4), the alkyl group for R _{1 to} R ₅ includes a linear or branched alkyl group, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. , And more preferably methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. As the cycloalkyl group in R _{1 to} R ₅ , those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group are preferable. R
The alkenyl group for _{1 to} R ₅ has 2 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group and hexenyl group.
Individual ones are preferred. Examples of the ring formed by combining two members out of R _{1 to} R ₅ include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring and a cyclooctane ring. In the general formulas (I-1) and (I-2), R _{1 to} R ₅ may be linked to any of the 7 carbon atoms forming the cyclic skeleton.

Further, as a further substituent of the above alkyl group, cycloalkyl group and alkenyl group, a carbon number of 1 to
Examples thereof include four alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like. Preferred examples of the repeating unit having a group represented by formulas (I-1) to (I-4) include a repeating unit represented by the following formula (AI).

[0085]

[Chemical 37]

In general formula (AI), R has the same meaning as R in general formula (a) described later. A'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. B represents a group represented by any one of formulas (I-1) to (I-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0087]

[Chemical 38]

In the above formula, Ra, Rb and r1 are as defined below. m represents an integer of 1 to 3.
Specific examples of the repeating unit represented by formula (AI) are shown below, but the content of the present invention is not limited thereto.

[0089]

[Chemical Formula 39]

[0090]

[Chemical 40]

[0091]

[Chemical 41]

[0092]

[Chemical 42]

[0093]

[Chemical 43]

[0094]

[Chemical 44]

[0095]

[Chemical formula 45]

In the present invention, the resin (B) is further protected with at least one group selected from the groups having an alicyclic hydrocarbon structure represented by the above general formulas (pI) to (pVI). It is preferable to contain a repeating unit having an alkali-soluble group in that the effect of the present invention becomes more remarkable.
In formulas (pI) to (pVI), the alkyl group for R _{12 to} R ₂₅ may be substituted or unsubstituted, and is a linear or branched alkyl group having 1 to 4 carbon atoms. Represents Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Further, as the further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group, alkoxycarbonyl group,
A nitro group etc. can be mentioned. The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic.
Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among the groups containing an alicyclic hydrocarbon structure.

[0097]

[Chemical formula 46]

[0098]

[Chemical 47]

[0099]

[Chemical 48]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

The substituents on these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a cycloalkyl group,
Examples thereof include an alkenyl group, an acyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. As the alkyl group, a methyl group, an ethyl group,
Lower alkyl groups such as propyl group, isopropyl group and butyl group are preferable, more preferably methyl group, ethyl group,
A propyl group and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. As the alkoxy group (including the alkoxy group of the alkoxycarbonyl group), a methoxy group,
C1-C1 such as ethoxy, propoxy, butoxy
There can be four. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like. Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, and specific examples thereof include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group. Examples of the acyl group include acetyl group, ethylcarbonyl group and propylcarbonyl group. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom.

Among the structures represented by the general formulas (pI) to (pVI), the general formula (pI) is preferable, and the group represented by the general formula (pIa) is more preferable. The alkyl group represented by R ₂₈ in formula (pIa), the halogen atom represented by R _{29 to} R ₃₁ , an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acyl group are the alicyclic hydrocarbon groups. Examples of the substituents are listed.

In the above resins, the general formulas (pI) to (pV)
Examples of the alkali-soluble group protected by the structure represented by I) include various groups known in the technical field. Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group, with a carboxylic acid group and a sulfonic acid group being preferred. The alkali-soluble group protected by the structures represented by the general formulas (pI) to (pVI) in the resin is preferably the following general formula (pVI).
Examples thereof include groups represented by I) to (pXI).

[0104]

[Chemical 49]

Here, R _{11 to} R ₂₅ and Z are the same as defined above. The repeating unit represented by the following general formula (pA) is preferable as the repeating unit having an alkali-soluble group protected by the structure represented by any of the general formulas (pI) to (pVI), which constitutes the above resin.

[0106]

[Chemical 50]

In the general formula (pA); R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. Examples of the halogen atom and alkyl group of R may be the same as those of R in the general formula (a) described later. A ′ has the same meaning as above. Ra is
It represents any group of the above formulas (pI) to (pVI). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) will be shown.

[0108]

[Chemical 51]

[0109]

[Chemical 52]

[0110]

[Chemical 53]

[0111]

[Chemical 54]

[0112]

[Chemical 55]

[0113]

[Chemical 56]

The resin (B) may further contain another repeating unit. The resin (B) in the present invention preferably contains the repeating unit represented by the general formula (a) as another copolymerization component. This improves developability and adhesion to the substrate. Examples of the alkyl which may have a substituent of R in the general formula (a) include the general formula (I-
The same examples as R ₁ in 1) to (I-4) can be given. Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. At least one of R _{32 to} R _{34 in} the general formula (a) is a hydroxyl group, preferably a dihydroxy body or a monohydroxy body, and more preferably a monohydroxy body.

Further, the resin (B) in the present invention contains the following general formulas (III-a) to (II) as other copolymerization components.
It preferably contains a repeating unit represented by I-d). This improves the resolution of the contact hole pattern.

[0116]

[Chemical 57]

In the above formula, R₁Is synonymous with R above.
R_Five~ R₁₂Each independently have a hydrogen atom or a substituent
It represents an optional alkyl group. R is a hydrogen atom or
Is an alkyl group which may have a substituent, a cyclic alkyl group
It represents a kill group, an aryl group or an aralkyl group. m is 1
Represents an integer of -10. X has a single bond or a substituent
Optionally, alkylene group, cyclic alkylene group, ari
Group, ether group, thioether group, cal group
Bonyl group, ester group, amide group, sulfonamide
Group selected from the group consisting of a group, a urethane group, and a urea group.
Germany or a combination of at least two of these groups
And a divalent group that is not decomposed by the action of an acid. Z
Is a single bond, an ether group, an ester group, an amide group, an
It represents a xylene group or a divalent group in which these are combined.
R₁₃Is a single bond, an alkylene group, an arylene group, or
It represents a divalent group in which these are combined. R₁₅Is Alkyre
Group, arylene group, or divalent combination thereof.
Represents a group. R₁₄Is an optionally substituted alkyl
Group, cyclic alkyl group, aryl group or aralkyl group
You R ₁₆Is a hydrogen atom or has a substituent
Good alkyl group, cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. A is the official shown below
Represents any of the functional groups.

[0118]

[Chemical 58]

Examples of the alkyl group represented by R _{5 to} R ₁₂ , R, R ₁₄ and R ₁₆ include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. , And more preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, heptyl group,
An octyl group, a nonyl group, and a decyl group. R, R ₁₄ , R
_Examples of the cyclic alkyl group of ₁₆ include those having 3 to 30 carbon atoms, specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group. , A dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, a steroid residue and the like.

Examples of the aryl group of R, R ₁₄ and R ₁₆ include those having 6 to 20 carbon atoms, which may have a substituent. Specific examples thereof include a phenyl group, a tolyl group and a naphthyl group. Examples of the aralkyl group of R, R ₁₄ and R ₁₆ include those having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a cumyl group and the like, which may have a substituent. The alkenyl group for R ₁₆ has 2 carbon atoms.
To 6 alkenyl groups, specifically, vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, 3-oxocyclohexenyl group, 3-oxo. Examples thereof include a cyclopentenyl group and a 3-oxoindenyl group. Of these, the cyclic alkenyl group may contain an oxygen atom.

As the linking group X, an alkylene group, a cyclic alkylene group, an arylene group which may have a substituent, or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, urethane Group, a single group selected from the group consisting of urea groups, or a combination of at least two or more of these groups,
A divalent group which is not decomposed by the action of an acid can be mentioned. Z
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group combining these. Examples of the arylene group in X, R ₁₃ and R ₁₅ include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, a phenylene group, a tolylene group,
Examples thereof include naphthylene group. Examples of the cyclic alkylene group for X include those in which the above-mentioned cyclic alkyl group is divalent.

Examples of the alkylene group in X, Z, R ₁₃ and R ₁₅ include groups represented by the following formula. -[C (Ra) (Rb)] r1-In the formula, Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r1 represents an integer of 1 to 10. Specific examples of the linking group X are shown below, but the contents of the present invention are not limited thereto.

[0123]

[Chemical 59]

Further substituents on the above alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include a carboxyl group, an acyloxy group, a cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples thereof include an alkoxy group, an acetylamide group, an alkoxycarbonyl group and an acyl group. Examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. An acetoxy group etc. are mentioned as an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

Specific examples of the structure of the side chain in the general formula (III-b) are shown below, but specific examples of the structure of the terminal excluding X are shown below, but the contents of the present invention are not limited thereto. .

[0126]

[Chemical 60]

Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III-c) are shown below.
The contents of the present invention are not limited to these.

[0128]

[Chemical formula 61]

[0129]

[Chemical formula 62]

[0130]

[Chemical formula 63]

Specific examples of the repeating structural unit represented by formula (III-d) are shown below, but the contents of the present invention are not limited thereto.

[0132]

[Chemical 64]

[0133]

[Chemical 65]

[0134]

[Chemical formula 66]

In the general formula (III-b), R _{5 to} R _5
12 is preferably a hydrogen atom or a methyl group. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is preferably 1 to 6. In formula (III-c), R ₁₃ is preferably an alkylene group such as a single bond, a methylene group, an ethylene group, a propylene group or a butylene group, and R ₁₄ is a methyl group, an ethyl group or the like having 1 carbon atom.
-10 alkyl groups, cyclopropyl groups, cyclohexyl groups, cyclic alkyl groups such as camphor residues, naphthyl groups and naphthylmethyl groups are preferred. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond. In formula (III-d), R ₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. R ₁₆ is an optionally substituted alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group and an octyl group, a cyclohexyl group, Adamantyl group, norbornyl group, boronyl group, isobornyl group,
Menthyl group, morpholino group, 4-oxocyclohexyl group and optionally substituted phenyl group, toluyl group, mesityl group, naphthyl group and camphor residue are preferable. As these further substituents, a halogen atom such as a fluorine atom and an alkoxy group having 1 to 4 carbon atoms are preferable. In the present invention, general formula (III-a) to general formula (III
-D), general formula (III-b) and general formula (II
The repeating unit represented by Id) is preferred.

In addition to the above, the resin (B) controls dry etching resistance, suitability for standard developing solution, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general requirements for resist. It can be used as a copolymer with various monomer repeating units for the purpose.

Examples of such repeating units include, but are not limited to, repeating units corresponding to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film-forming property (glass transition point), (3)
Alkali developability, (4) Membrane slippage (hydrophobicity, selection of alkali-soluble groups), (5) Adhesion of unexposed area to substrate,
(6) It is possible to finely adjust the dry etching resistance.
Examples of such copolymerizable monomers include addition polymerizable unsaturated bonds selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. The compound etc. which have one can be mentioned.

Specifically, for example, acrylic acid esters such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0) is preferred) Acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic acid-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate etc.);

Methacrylic acid esters, for example, alkyl (alkyl groups preferably having 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethylmethacrylate, propylmethacrylate, isopropylmethacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.); acrylamides such as acrylamide, N-alkylacrylamide , (Alkyl group has 1 to 1 carbon atoms
0, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group and the like. ), N,
N-dialkyl acrylamide (alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group,
There are butyl group, isobutyl group, ethylhexyl group, cyclohexyl group and the like. ), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N
-Acetylacrylamide etc .;

Methacrylamides, such as methacrylamide, N-alkylmethacrylamides (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl). Groups, etc.), N, N-dialkylmethacrylamides (such as ethyl groups, propyl groups, and butyl groups as alkyl groups), N-hydroxyethyl-N-methylmethacrylamide, etc .; allyl compounds such as allyl esters ( For example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc .; vinyl ethers such as alkyl vinyl ethers (eg, Hex Vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, etc .; dialkyl itaconates (eg dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid etc.); dialkyl esters of fumaric acid (eg dibutyl Fumarate etc.) or monoalkyl esters; other acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleironitrile. In addition, addition polymerizable unsaturated compounds copolymerizable with the above various repeating units may be used. In the resin of (B), the content molar ratio of each repeating unit structure is generally required for the acid value, the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the density dependence of the resist profile, and the resist. It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, etc.

In the resin (B), the compounds represented by the general formulas (I-1) to (I
-4) content of the repeating unit having a group represented by
It is 30 to 70 mol% in all repeating units, preferably 35 to 65 mol%, and more preferably 40 to 60 mol%. The content of the repeating unit having a group represented by any one of formulas (pI) to (pVI) is as follows.
It is usually 20 to 75 mol%, preferably 25 to 70 mol%, more preferably 30 to 65 mol%. (B)
In the resin, the content of the repeating unit represented by the general formula (a) is usually 0 mol% to 70 mol% in all the monomer repeating units.
It is preferably 10 to 40 mol%, more preferably 15 to 30 mol%. In addition, the content of the repeating units represented by the general formulas (III-a) to (III-d) in the resin (B) is usually 0.
1 mol% to 30 mol%, preferably 0.5 to 25
Mol%, more preferably 1 to 20 mol%.

The content of the repeating unit based on the monomer of the above-mentioned additional copolymerization component in the resin can be appropriately set according to the desired performance of the resist. Repeating units containing a group represented by any one of (I-1) to (I-4) and general formulas (pI) to (pI).
It is preferably 99 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, based on the total number of mols of the repeating units having a group represented by VI). The weight average molecular weight Mw of the resin (B) is a polystyrene standard by gel permeation chromatography, preferably 1,000 to 1,000,000.
0, more preferably 1,500 to 500,000, further preferably 2,000 to 200,000, and particularly preferably 2,500 to 100,000. The larger the weight average molecular weight, the higher the heat resistance. While improving, the developability and the like decrease, and the balance is adjusted to a preferable range. The resin (B) used in the present invention can be synthesized by a conventional method, for example, a radical polymerization method. Hereinafter, specific examples of the resin (B) of the present invention will be listed, but the contents of the present invention are not limited thereto.

[0144]

[Chemical formula 67]

[0145]

[Chemical 68]

[0146]

[Chemical 69]

[0147]

[Chemical 70]

[0148]

[Chemical 71]

[0149]

[Chemical 72]

[0150]

[Chemical formula 73]

[0151]

[Chemical 74]

[0152]

[Chemical 75]

[0153]

[Chemical 76]

[0154]

[Chemical 77]

[0155]

[Chemical 78]

[0156]

[Chemical 79]

[0157]

[Chemical 80]

[0158]

[Chemical 81]

[0159]

[Chemical formula 82]

In the above formula, m, n, p, and n1, n
2 and n3 each represent the molar ratio of the number of repetitions. (I-
The repeating unit having a group represented by any one of 1) to (I-4) is represented by n, and when two or more kinds are combined, n is represented.
They are distinguished by 1, n2, etc. The repeating unit having a group containing an alicyclic hydrocarbon structure represented by (pI) to (pVI) is represented by m. Formulas (III-a) to (III-
The repeating unit represented by d) is represented by p. When the repeating units represented by formulas (III-a) to (III-d) are included, m / n / p is (25 to 70) / (25
~ 65) / (3-40). General formula (III-a)
-(III-d) does not contain the repeating unit, m / n is (30-70) / (70-30). It may be a block copolymer or a random copolymer.
It may be a regular polymer or an irregular polymer.

In the positive photoresist composition for deep UV exposure of the present invention, the amount of the resin (B) added in the entire composition is preferably 40 to 99.99% by weight, more preferably total resist solids. Is 50 to 99.97% by weight.

In the positive resist composition of the present invention, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
A surfactant, a photosensitizer, an organic basic compound, a compound that promotes solubility in a developing solution, and the like can be contained. The positive photoresist composition of the present invention preferably contains a surfactant, and particularly preferably contains a fluorine-based and / or silicon-based surfactant.

That is, it is particularly preferable to contain any one or two or more of a fluorine type surfactant, a silicon type surfactant and a surfactant containing both a fluorine atom and a silicon atom. Examples of these surfactants include JP-A-62-36663 and JP-A-61-226746.
No. 61-226745, 62-170.
950, JP-A-63-34540, JP-A-7-23.
No. 0165, JP-A-8-62834, JP-A-9-54
The surfactants described in JP-A No. 432 and JP-A-9-5988 can be mentioned, and the following commercially available surfactants can be used as they are. As a commercially available surfactant that can be used,
For example, F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F17
3, F176, F189, R08 (Dainippon Ink Co., Ltd.)
Manufactured), Surflon S-382, SC101, 102, 1
03, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and the like, and fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-34
1 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The content of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

Specific examples of the surfactants that can be used include polyoxyethylene such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. Alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate , Sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene Nonionics such as polyoxyethylene sorbitan fatty acid esters such as bitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate A surfactant and the like can be mentioned. The amount of these other surfactants to be added is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition of the present invention.

The acid diffusion inhibitor (C) that can be used in the present invention is preferably added from the viewpoint of suppressing fluctuations in sensitivity and resolution with time after heating after exposure and development processing, and preferably organic bases. It is a sex compound. Examples of the organic basic compound include nitrogen-containing basic compounds having the following structures.

[0167]

[Chemical 83]

Here, R ²⁵⁰ , R ^251, and R ²⁵² are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R
²⁵² may combine with each other to form a ring.

[0169]

[Chemical 84]

(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and each represents an alkyl group having 1 to 6 carbon atoms.) A more preferable compound is a nitrogen-containing basic compound having two or more nitrogen atoms of different chemical environments in one molecule,
Particularly preferred is a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted amino An alkyl morpholine etc. are mentioned. Preferred substituents are amino groups, aminoalkyl groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups, alkoxy groups, acyl groups, acyloxy groups, aryl groups, aryloxy groups, nitro groups,
A hydroxyl group and a cyano group.

Preferred specific compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 1- (2-
Aminoethyl) pyrrolidine, pyrazole, 3-amino-
5-methylpyrazole, 5-amino-3-methyl-1-
p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU) and the like 3
Grade morpholine derivatives, hindered amines described in JP-A No. 11-52575 (for example, the publication [0005]
And the like) but are not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2]. 2.2.2] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMETU
And tertiary hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Among them, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
1,4-diazabicyclo [2,2,2] octane, 4-
Dimethylaminopyridine, hexamethylenetetramine,
CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is preferred.

These nitrogen-containing basic compounds may be used alone or in combination of two or more. The nitrogen-containing basic compound is used in an amount of usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total solid content of the photosensitive resin composition. If it is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

The positive resist composition of the present invention is dissolved in a solvent which dissolves each of the above components and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone,
γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, lactic acid Ethyl, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Among the above, the preferable solvent is 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, methoxypropionic acid Mention may be made of methyl, ethyl ethoxypropionate, N-methylpyrrolidone and tetrahydrofuran. It is also preferable to mix two or more solvents, and particularly preferably a mixed solvent of a solvent not containing a hydroxyl group and a solvent containing a hydroxyl group.

The positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably 0.2 to 1.2 μm. In the present invention,
If necessary, a commercially available inorganic or organic antireflection film can be used. As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type composed of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum vapor deposition apparatus, a CVD apparatus, and a sputtering apparatus for forming a film. Examples of the organic antireflection film include Japanese Patent Publication No. 7-
What is composed of a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in 69611, an alkali-soluble resin and a light absorber, a reaction product of a maleic anhydride copolymer and a diamine type light absorber described in US Pat. No. 5,294,680. A resin containing the resin binder described in 118631 and a methylol melamine-based thermal cross-linking agent.
-118656, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light-absorbing group in the same molecule, comprising a methylol melamine and a benzophenone-based light-absorbing agent described in JP-A-8-87115, and JP-A-8-17950.
Examples of the polyvinyl alcohol resin described in 9 include a low molecular weight light absorber. In addition, as the organic antireflection film, DUV30 series and DUV-40 series manufactured by Brewer Science Co., AC-2 manufactured by Shipley Co.,
AC-3 etc. can also be used.

The resist solution is applied onto a substrate (eg, a silicon / silicon dioxide coating) (such as a substrate optionally provided with the above antireflection film), a spinner, or a coater which is used in the manufacture of precision integrated circuit devices. A good resist pattern can be obtained by applying a suitable coating method such as the above, exposing through a predetermined mask, baking and developing. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157
nm), X-rays, electron beams and the like.

As the developing solution, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc.,
Primary amines such as ethylamine and n-propylamine,
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. It is possible to use an alkaline aqueous solution of a quaternary ammonium salt, a cyclic amine such as pyrrole, or a pyrhelidine. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0179]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[Synthesis of Photoacid Generator as Component (A)] Two synthetic examples of the photoacid generator as Component (A) are shown below. Other photoacid generators used below Was synthesized by a similar method, the above-mentioned general method, or a commercially available one was used. The following photo-acid generator was manufactured by Midori Kagaku Co., Ltd. Triphenylsulfonium perfluoro-n-butanesulfonate: (A1-1), (A2-4) Triphenylsulfonium trifluoromethanesulfonate: (A2-1) Bis (t-butylphenyliodonium) perfluoro-
n-Butane sulfonate: (A1-49)

[Triphenylsulfonium Perfluoro-
Synthesis of n-octane sulfonate (A1-3)] 50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, 400 ml of concentrated hydrochloric acid was added, and the mixture was heated at 70 ° C for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, filtered, and then 200 g of ammonium iodide dissolved in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate, and dried to obtain 70 g of triphenylsulfonium iodide. Dissolve 17.6 g of triphenylsulfonium iodide in 1000 ml of methanol,
12.5 g of silver oxide was added to this solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered, and 25 g of perfluoro-n-octanesulfonic acid in methanol was added thereto. The reaction solution was concentrated, the precipitated oily substance was dissolved in ethyl acetate, washed with water, dried and concentrated to obtain 20.5 g of the desired product.

[(Tri (t-butylphenyl) sulfonium perfluoro-n-butanesulfonate (A1-5)
And (A2-8) Synthesis] Di (t-butylphenyl) sulfide (80 mmol), di (t-butylphenyl)
Iodonium perfluoro-n-butane sulfonate (2
A mixture of 0 mmo1) and copper benzoate (4 mmo1) was stirred under a nitrogen stream at 130 ° C. for 4 hours. Allow the reaction solution to cool,
100 ml of ethanol was added to this, and the deposit was removed.
The filtrate was concentrated, and 200 ml of ether was added to this to precipitate a powder, which was collected by filtration, washed with ether and dried to obtain the desired product.

[Synthesis of Resin Example (1) of the Present Invention] 2-Methyl-2-adamantyl methacrylate and 6-endo-
Hydroxybicyclo [2.2.1] heptane-2-en
N-N was prepared by charging do-carboxylic acid-γ-lactone with 5-exo-methacrylate at a molar ratio of 50/50.
-Dimethylacetamide / tetrahydrofuran = 5/5
100 ml of a solution having a solid content of 20% was prepared. 6-endo-hydroxybicyclo [2.2.1]
The 5-exo-methacrylate of heptane-2-endo-carboxylic acid-γ-lactone is 6-endo-hydroxybicyclo [2.2.1] heptane-2-endo-.
A product obtained by acetoxy-lactonizing a carboxylic acid, alkali-hydrolyzing an acetoxy group into a hydroxy group, and esterifying with methacrylic acid chloride was used. J. Chem. Soc. , 227 (195
9), Tetrahedron, 21, 1501 (19)
65) According to the method described. To this solution, 3 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 10 ml of N, N-dimethylacetamide heated to 60 ° C. in a nitrogen atmosphere for 3 hours. After completion of the dropping, the reaction solution was heated for 3 hours, 1 mol 1% of V-65 was added again, and the mixture was stirred for 3 hours. After the reaction is completed, the reaction solution is cooled to room temperature and distilled water 3 L
The white powder which was crystallized and precipitated was recovered. The polymer composition determined from C ¹³ NMR was 51/49. Also, GP
The weight average molecular weight in terms of standard polystyrene determined by C measurement was 7,200.

The resin examples (2) to (59) shown above were synthesized in the same manner as the above synthesis example. The molar ratio of the repeating units in Table 1 (the order from the left of the repeating units shown in each resin example)
And the weight average molecular weight are shown.

[0185]

[Table 1]

[0186]

[Table 2]

Examples 1 to 59 and Comparative Examples 1 to 5 [Preparation and Evaluation of Photosensitive Composition] The resin synthesized in the above Synthesis Example and each component shown in Table 2 are shown in Table 2 at a solid content of 12% by weight. After being dissolved in the solvent described in 1., the positive resists of Examples 1 to 59 and Comparative Examples 1 to 5 were prepared by filtering with a 0.1 μm microfilter. Table 2 shows each component of the composition of the present invention used.

[0188]

[Table 3]

[0189]

[Table 4]

Each symbol in Table 2 shows the following. [Resin] Resin Z: 2-methyl-2-adamantyl methacrylate mevalonic lactone methacrylate (50/5
0), weight average molecular weight 6900 [acid diffusion inhibitor] B1: DBN; 1,5-diazabicyclo [4.3.0]
Nona-5-ene B2: TPI; 2,4,5-triphenylimidazole B3: DCMA; Dicyclohexylmethylamine B4: 2,6-diisopropylaniline B5: TPSA; Triphenylsulfonium acetate

[Surfactant] W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine type) W2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine and silicon type) W3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Silicone type) W4: Troisol S-366 (Troy Chemical Co., Ltd.)
Made)

[Solvent] PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether CH: Cyclohexanone BL: γ-butyrolactone

<Image Evaluation Method> (1) Evaluation of Resolving Power, Exposure Margin, Dependence of Spatial Density, and Line Edge Roughness On a silicon substrate treated with hexamethyldisilazane with a spin coater, an antireflection film DUV- manufactured by Brewer Science Co., Ltd. 42 was evenly applied at 600 angstrom, dried at 100 ° C. for 90 seconds on a hot plate, and then heated and dried at 190 ° C. for 240 seconds. afterwards,
Each photosensitive resin composition is applied with a spin coater and the temperature is 120 ° C.
And dried for 90 seconds to form a 0.3 μm resist film. An ArF excimer laser stepper (NA = 0.6 manufactured by ISI) is passed through the resist film through a mask.
And then immediately heated on a hot plate at 120 ° C. for 90 seconds. Further, it was developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds and then dried to obtain a resist line pattern.

[Resolving power]: The resolving power shows a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.13 μm. [Exposure margin]: The exposure amount that reproduces a 0.13 μm line-and-space (1/1) mask pattern is the optimum exposure amount, and the exposure amount width that reproduces a line width of 0.13 μm ± 10% is the optimum exposure amount. The value divided by was expressed as a percentage (%). The larger the number, the smaller the change in line width with respect to the change in exposure amount. [Dense / dense dependence] Line and space pattern with line width 0.13 μm (Dense pattern: line and space 1 /
1) and an isolated line pattern (sparse pattern: line and space 1/5), each 0.13 μm ± 1
The overlapping range of the depth of focus that allowed 0% was obtained. The larger this range is, the better the density dependence is. [Line edge roughness] Measure the distance from the reference line where the edge should be within the range of 5 μm in the longitudinal direction of the isolated line pattern. SEM (Hitachi Ltd. S-
8840), 50 points were measured, the standard deviation was calculated, and 3σ was calculated. The smaller the value, the better the performance. The results are shown in Table 3.

[0195]

[Table 5]

[0196]

[Table 6]

As is clear from the results shown in Table 3, the positive resist composition of the present invention is at a satisfactory level for all of them. That is, it is suitable for lithography using deep ultraviolet rays such as ArF excimer laser exposure.

[0198]

INDUSTRIAL APPLICABILITY The present invention can provide a positive resist composition which is suitable for far ultraviolet light, particularly ArF excimer laser light, and is excellent in resolution, exposure margin, dependency of density and line edge roughness.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA02 AA03 AB16 AC04 AC08                       AD03 BE07 BG00 FA03 FA12                       FA17

Claims (6)

[Claims] 1. A cation part (A) is composed of iodonium or sulfonium, and an anion part is R ^F SO ₃ ^— (wherein
R ^F is a fluorine-substituted alkyl group having 1 to 20 carbon atoms) and is selected from a sulfonate composed of anions represented by, and the difference in carbon number of R ^F of the anion portion is 2 to 2. A photoacid generator capable of generating an acid upon irradiation with at least two actinic rays or radiations in the range of 15 and (B) represented by at least one of the following general formulas (I-1) to (I-4) A positive photoresist composition, comprising a resin containing a repeating unit having a group, which is decomposed by the action of an acid to increase the solubility in alkali. [Chemical 1] In formulas (I-1) to (I-4), R _{1 to} R ₅ may be the same or different, and may be a hydrogen atom or a substituent, an alkyl group, a cycloalkyl group or an alkenyl. Represents a group. Two of R _{1 to} R ₅ may combine with each other to form a ring. About wherein component (A), a linear fluorine-substituted alkyl as the photoacid generator R ^F anion portion is in the range of 4 to 20 carbon atoms the carbon number of R ^F is relatively large is selected from the group of the photoacid generator is a group, linear fluorocarbon as the photoacid generator carbon number of R ^F is relatively small where R ^F anion portion is in the range of 1 to 5 carbon atoms The positive photoresist composition according to claim 1, wherein the positive photoresist composition is selected from the group of photoacid generators that are substituted alkyl groups. 3. The positive resist according to claim 1, wherein the cation moiety of at least one photoacid generator is represented by the following general formula (I), (II) or (III). Composition. [Chemical 2] In the general formulas (I) to (III), R _{1 to} R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group. , A halogen atom, or a —S—R ₃₈ group. R
₃₈ represents a linear, branched or cyclic alkyl group or aryl group. In addition, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R ₂₈ to
Two or more of R ₃₇ may be bonded to each other to form a ring containing one kind or two or more kinds selected from a single bond, carbon, oxygen, sulfur and nitrogen. 4. The resin of (B) further has the following general formula (p
I) to (pVI), which contains a repeating unit having an alkali-soluble group protected by at least one group selected from the groups having an alicyclic hydrocarbon structure represented by I to (pVI). The positive photoresist composition as described in any one of 3 above. [Chemical 3] In formulas (pI) to (pVI), R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z
Represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R ₁₂ to R ₁₆ each independently of 1 to 4 carbon atoms, a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R _14, or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ are each independently a hydrogen atom,
It represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Also, R ₁₉ ,
Any of R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ ~ R
Each ₂₅ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that
At least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. 5. Represented by the general formulas (pI) to (pVI)
A group containing an alicyclic hydrocarbon structure represented by the following general formula (pI
It is a group represented by a), It is characterized by the above-mentioned.
The positive photoresist composition as described in any one of 1. [Chemical 4] R in the general formula (pIa)₂₈May have a substituent
Represents an alkyl group. R ₂₉~ R₃₁Are the same or different
May be, hydroxy group, halogen atom, carboxy group
Alternatively, an alkyl group which may have a substituent, a group
Chloroalkyl group, alkenyl group, alkoxy group, alcohol
Represents a oxycarbonyl group or an acyl group. p, q, r are
Each independently represents an integer of 0 or 1 to 3. 6. The resin of (B) has the following general formula (a):
The positive photoresist composition according to claim 1, further comprising a repeating unit represented by: [Chemical 5] In general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R _{32 to} R _{34, which} may be the same or different, each represents a hydrogen atom or a hydroxyl group. At least one of R _{32 to} R ₃₄
One represents a hydroxyl group.